Hardening compositions with pyrazolone couplers



United States Patent Ofiice 3,359,111 Patented Dec. 19, 1967 3 359,111 HARDENING COMPOSITIONS WITH PYRAZOLONE COUPLERS John H. Van Campen, Rochester, N.Y., assiguor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N Drawing. Filed Aug. 27, 1965, Ser. No. 483,332

Claims. (Cl. 96-100) ABSTRACT OF THE DISCLOSURE Photographic products useful in preparing color prints in which staining is inhibited comprising a gelatin-silver halide photographic emulsion, a pyrazolone coupler and a bis(beta-acyloxyethyl)-ketone, such as 1,5-diacetoxy-3- pentanone and 1,10-diacetoxy-3,S-decanedione, for example.

This invention relates to photographic products useful for color prints in which staining is inhibited comprising gelatin-silver halide photographic emulsions, pyrazolone coupler and a compound on the order of bis(beta-acyloxyethyl)ketone as a hardener for gelatin.

In the making of photographic color prints using gelatin layers containing silver halide and couplers which form a magenta image, staining has often occurred. The commonly used gelatin hardeners do not prevent and in many cases may even promote the staining of paper or other supports upon which these layers are applied. As a consequence, the quality of the prints obtained may be adversely affected.

One object of my invention is to provide photographic products adapted to the making of color prints in which staining effects are inhibited and the sensitometric properties are not adversely affected. Another object of my invention is to provide photographic products containing gelatin-silver halide photographic emulsions, pyrazolone couplers and as a gelatin hardener a certain type of ketone.

I have found that photographic products featuring the combination of emulsions having silver halide as the photosensitive element, a pyrazolone coupler which is capable of forming an azornethine dye with a phenylenediamine developer and a hardener having the following general formula:

XCH CH CO [ACO] CHgCHzX in which X is an acyloxy radical of 2-5 carbon atoms which may or may not be halogen containing; m=0 or 1; A is a divalent linkage selected from the group consisting of (CR per se and (CR in which at least one CR unit is replaced by a replacement of CR=CR, O-, S, arylene or cycloalkylene radicals; and R is a hydrogen or alkyl group of 1-4 carbon atoms, will be free of staining when that combination is present on a paper support in its use for making photographic prints. My invention is useful with pyrazolone couplers such as those described in US. Patent 2,640,776 of Spence and Carroll or US. Patent 2,600,788 of Loria et al.

The compounds which may be employed as hardeners in color emulsions in accordance with my invention are ketone hardeners as are described in more detail in Burness and Wilson application Ser. No. 379,018, filed June 29, 1964. I have found that combinations containing pyrazolone coupler silver halide emulsion and hardener, the latter being of the type described in Ser. No. 379,018, have good brightness characteristics and are more free of stain than compositions of like nature but of a type that has been formerly used. Layers in accordance with my invention show reduced stain and no adverse sensitometric effect when a bis(beta-acyloxyethyl) ketone is used in a proportion which produces satisfactory hardness in layers containing gelatin, silver halide, and a coupler material. No effect upon dye hue or stability of the photographic product has been observed either as a result of the various components of the materials used or of the retention of processing chemicals. My invention avoids the obtaining of stain generally and if any staining should occur it will be only a neutral stain of the lowest possible density.

In the emulsions in accordance with my invention gelatin is primarily employed as the vehicle for the silver halide. However, if desired the presence of polymers auxiliary to the gelatin may be present such as ethyl acrylate-acrylic acid copolymer or butyl acrylate-acrylic acid copolymer or some other acid substituted polymeric vehicle. Not only does my invention relate to color emulsions in which pyrazolone coupler is present but also included are color emulsions in which the coupler is provided from solution in some water immiscible solvent so as to constitute a package form of emulsion. My invention includes any of the recognized color photographic emulsions having silver halide as the photosensitive element, pyrazolone coupler and a hardener of the type described and claimed in Ser. No. 379,018. My invention includes combinations composed of silver halide emulsion, hardener of the type described and claimed in Ser. No. 379,018 and pyrazolone coupler (1) when all three of these components are in a single emulsion or (2) when one or more of these components are in a layer other than that containing one or more of these components as for example a multi-layer system in which one of the components is in a layer with or without one or both of the other members of the combination.

The following example illustrates the advantage of my invention in the obtaining of photographic prints from material using compositions in accordance with my invention.

Example This example illustrates photographic color print material uSing two different types of ketone hardeners in a multilayer photographic color product in which one of the emulsions contain both pyrazolone coupler and hardener in accordance with the invention. Also that hardener is used in the other five layers of the structure but pyrazolone coupler is absent. Also used in a multilayer product was aldehyde-type gelatin hardener for purposes of comparison.

A series of coatings were laid down upon a paper support as follows:

Layer 6gelatin layer.

Layer 5-red-sensitive silver chlorobromide gelatin consisting of 90 mole percent bromide-l-a phenolic cyan coupler of the type described in US. Patent 2,423,730.

Layer 4-gelatin layer+an ultraviolet absorber.

Layer 3-green-sensitive silver chlorobromide gelatin emulsion consisting of mole percent chloride+a pyrazolone magenta coupler of the type described in U.S. Patent 2,600,788.

Layer 2gelatin layer.

Layer 1blue-sensitive silver chlorobromide gelatin emulsion consisting of 98 mole percent bromide-{an acyl acetanilide yellow coupler of the type described in US. Patent 2,875,057.

Samples A, B and C were prepared. A was composed of the layers as outlined. In all of the layers of Sample A 0.54% of mucochloric acid (based on the weight of the gelatin) was used as the hardener. In Sample B each of the six layers contained 1% (by weight of the gelatin) of 1,5-diacetoxy-3-pentanone. Each of the six layers of Sample C contained 1.4% by weight of the gelatin of 1,10-

PERCENT REFLECTANCE FOR WAVELENGTH I'N MILLIMICR ONS Sample 420 440 460 480 A 60.5 67.2 71. 2 73.8 B 63. 70. 2 74. 2 77. 0 C 63. 5 70. 5 74. 4 77. 2

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

I claim:

1. A gelatin-silver halide photographic emulsion useful in color photography which contains a pyrazolone coupler capable of forming an azomethine dye with a phenylene diamine developer and a hardener having the formula in which X is selected from the group consisting of acetoxy and chloroacetoxy, m is either 0 or 1 and A is a divalent linkage selected from the group consisting of (CH -CH=CH-, CH CH OCH CH -CH CH SCH CH phenylene and cyclohexylene radicals.

2. A multilayer photographic product, in which at least one layer contains gelatin-silver halide photographic emulsion, at least one layer contains pyrazolone coupler and at least one layer contains a hardener having the formula in which X is selected from the group consisting of acetoxy and chloroacetoxy, m is either 0 or 1 and A is a divalent linkage selected from the group consisting of (CH CH=CH, -CH CH OCH CH CH CH SCH CH phenylene and cyclohexylene radicals.

3. A multilayer photographic product in which at least one layer contains gelatin-silver halide photographic emulsion, at least one layer contains pyrazolone coupler and at least one layer contains 1,5-diacetoxy-3-pentanone.

4. A multilayer photographic product in which at least one layer contains gelatin-silver halide photographic emulsion, at least one layer contains pyrazolone coupler and at least one layer contaings l,lO-diacetoxy-3,8- decanedione.

5. A gelatin-silver halide photographic emulsion which contains pyrazolone coupler and 1,5-diacetoxy-3-pentanone.

6. A gelatin-silver halide photographic emulsion which contains pyrazolone coupled and l,10-diacetoxy-3,8-decanedione.

7. A photographic element which comprises a support having thereon a plurality of layers in which at least one of said layers contain gelatin-silver halide photographic emulsion, at least one of said layers contains pyrazolone coupler and at least one of said layers contain a hardener having the formula XCH CH CO (ACO) CH CH X in which X is selected from the group consisting of acetoxy and chloroacetoxy, m is either 0 or 1 and A is a divalent linkage selected from the group consisting of -(CH CH=CH--, CH CH OCH CH CH CH SCH CH phenylene and cyclohexylene radicals.

8. A photographic element comprising a support hearing a plurality of layers which collectively contains silver halide, pyrazolone coupler and 1,5-diacetoXy-3-pentanone.

9. A photographic element comprising a support hearing a plurality of layers which collectively contains silver haled, pyrazolone coupler and 1,10'-diacetoxy-3,8-decanedione.

10. A photographic element comprising a support hearing a plurality of layers, one of which layers contains silver halide, pyrazolone coupler and a hardener having the formula XCHQCHZCO (ACO CH CH X in which X is selected from the group consisting of acetoxy and chloroacetoxy, m is either 0 or 1 and A is a divalent linkage selected from the group consisting of 1 10, -CH CH SOH CH phenylene and cyclohexylene radicals.

References Cited UNITED STATES PATENTS 3,140,177 7/1964 Welch 96-111 NORMAN G. TORCHIN, Primary Examiner.

I. H. RAUB'ITSCHEK, Assistant Examiner. 

1. A GELATIN-SILVER HALIDE PHOTOGRAPHIC EMULSION USEFUL IN COLOR PHOTOGRAPHY WHICH CONTAINS A PYRAZOLONE COUPLER CAPABLE OF FORMING AN AZOMETHINE DYE WITH A PHENYLENEDIAMINE DEVELOPER AND A HARDENER HAVING THE FORMULA 